Aniline alkylation for the introduction of an alkyl group onto the amino group of the aniline molecule, referred to as N-alkylation, or the addition of an alkyl group onto a carbon atom of the benzene ring, referred to as C-alkylation, has been extensively studied in that it is recognized that significant changes in the chemical and physical properties of aniline can be brought about by such alkylation. The alkylated compounds such as ortho-, para-, and meta-alkylaniline are useful in a variety of applications such as dyes, pharmaceuticals, anti-oxidants, plasticizers, herbicides, insecticides, plant growth agents, and vulcanization accelerators. A critical concern, however, in the alkylation of aniline is the selective production of specifically desired compounds. The different products of a mixture of products which are commonly formed during an alkylation reaction of aniline have very close physical constants such as boiling point, leading to difficulty in separation by conventional methods, such as distillation. In order to avoid the difficult and expensive separation or isolation of the components of a mixture, attempts have been made to provide selective alkylation processes. The selective formation of the para-alkylaniline is particularly desirable since in the conventional method of forming toluidines, toluene is nitrated which gives from 50-65% of the ortho product which, after reduction, gives ortho-toluidine as the major product.
It has been recognized in the prior art that the use of zeolites offer a convenient means of providing reaction selectivity. Thus,
U.S. Pat. No. 4,274,982 discloses zeolite catalysts useful in the selective alkylation of aromatic molecules, and in particular to a method of maintaining the high para-selectivity of zeolite catalysts. Examples of alkyl aromatics produced utilizing the zeolite catalyst are the dialkylbenzenes. The useful life of a para-selective zeolite catalyst is prolonged by (1) maintaining the zeolite catalyst at a temperature of at least 50.degree. C. or in an atmosphere substantially free of moisture; and (2) modifying the catalyst with at least 0.25% by weight of one or more difficultly reducible oxides. Additionally, the zeolite catalyst has a particular silica to aluminum ratio and constraint index.
Japanese Patent No. 53-28128 discloses anilines which are p-methylated by vapor phase contact of anilines with methanol in the presence of an alkali metal form of synthetic, and specifically a Y-type molecular sieve, zeolite catalyst to produce 2,4-xylidine.
U.S. Pat. No. 4,593,124 discloses, inter alia, a process for preparing an isomeric mixture of an alkyl substituted aniline by contacting at least one isomer of the alkyl substituted aniline with a zeolite catalyst.
U.S. Pat. No. 4,480,128 discloses, inter alia, a process for the manufacture of at least one of the ortho-, meta-, or para-toluidine compounds by treating a first charge containing at least one toluidine isomer with an isomerization catalyst and then isolating the desired isomer by selective adsorption to a zeolite catalyst. The isomerization catalyst or zeolite catalyst may be a synthetic zeolite of the pentasil type or an X or Y type zeolite. The patent discloses that the isomerization reaction can be carried out in the gas phase and that the catalyst can be fixed. The isomerization reaction is stated as proceeding in a very selective manner.
U.S. Pat. No. 4,554,380, a continuation of U.S. Pat. No. 4,480,128, discloses a method for making at least one of the ortho-, meta-, or para-toluidine compounds by contacting at least one of the toluidine isomers, other than the isomer(s) sought to be isolated, with an isomerization catalyst which is a synthetic zeolite of the pentasil type.
European Patent No. 92,103, as discussed in Chemical Abstracts, Vol. 100, paragraph 6057d, and U.S. Pat. No. 4,593,124, discloses individual toluidine isomers prepared by isomerizing isomer mixtures or pure undesired toluidine isomers over a pentasil type zeolite. The desired isomer is then separated by adsorption on an average to large pore size zeolite catalyst.
U.S. Pat. No. 3,868,420 discloses, inter alia, the production of a phenylamine alkylated in the ortho- and/or para- positions by alkyl groups comprising the steps of reacting the phenylamine with an alkanol in the vapor phase in the presence of an aluminum oxide/molybdenum oxide mixed catalyst.
U.S. Pat. No. 4,613,705 discloses, inter alia, the alkylation of aromatic amines with an alkanol in the presence of a mixed metal oxide alkylation catalyst consisting of at least 70% by weight of a Group V-B metal oxide and 30% by weight of stannic oxide. The patent discloses as prior art an article appearing in Waseda Daigaku Rikogaku Kenkyusho Hokoku by Takamiya et al, Vol. 69, pp. 21-25 (1975), which is stated as reporting the results of a study of the vapor phase catalytic N-methylation of aniline with methanol with certain transition metal zeolites as catalysts.
U.S. Pat. No. 4,599,449 discloses, inter alia, a process for alkylating aromatic amines comprising reacting an aromatic amine with an alkanol in the presence of a metal oxide alkylation catalyst consisting essentially of at least 70 mole percent of a Group VII-B metal oxide and no more than about 30 mole percent of a Group VIII metal oxide.
U.S. Pat. No. 4,582,936 discloses, inter alia, the production of a dimethyl amine by the gas phase reaction of ammonia and methanol over a zeolite catalyst. The patent discloses as prior art that various zeolites have come of interest in producing a specific amine, such as monomethyl amine or dimethyl amine, with high selectivity. Japanese Patent Publication No. 113747/1981 is referred to in the patent as disclosing a method for selectively obtaining the monomethyl amine from ammonia and methanol utilizing various zeolites inclusive of mordenite.
U.S. Pat. No. 3,751,504 discloses, inter alia, a process for effecting vapor phase alkylation of an aromatic hydrocarbon charge by contacting the aromatic hydrocarbon charge with an alkylating agent in the presence of a catalyst characterized by a particular x-ray diffraction pattern. The catalyst claimed belongs to the family of zeolites known as Zeolite ZSM-5 stated to be suitable alkylating agents.
U.S. Pat. No. 3,751,506 discloses, inter alia, a process for effecting vapor phase alkylation of an aromatic hydrocarbon charge with an alkylating agent in the presence of a crystalline aluminum silicate zeolite having a specific formula under specific reaction conditions. The catalyst useful in the disclosed invention belongs to the family of zeolites known as Zeolite ZSM-5.
U.S. Pat. No. 3,755,483 discloses, inter alia, the process for effecting the vapor phase alkylation of a hydrocarbon charge with an alkylating agent in the presence of a zeolite catalyst having a specific x-ray diffraction pattern. The catalyst useful in the invention is known as Zeolite ZSM-12.
U.S. Pat. No. 4,613,717 discloses, inter alia, a process for producing a 1,4-dialkylbenzene comprising contacting benzene or a monoalkylbenzene with an alkylating agent in the vapor phase in the presence of a zeolite catalyst.
U.S. Pat. No. 3,598,878 discloses, inter alia, a process for the alkyl transfer of an alkyl aromatic comprising contacting an alkyl aromatic feed material with a catalyst comprising vanadium deposited on a zeolite base.
U.S. Pat. No. 3,597,491 discloses, inter alia, a process for the alkyl transfer of alkyl aromatics comprising contacting an alkyl aromatic feed material with a catalyst comprising a Group VI-B metal deposited on a type Y zeolite base.
U.S. Pat. No. 4,599,473 discloses, inter alia, a process for the selective alkylation of a monoalkylbenzene into a dialkylbenzene utilizing a silica catalyst of the silicalite type. The patent discloses as prior art that various alumino-silicate type zeolite catalysts, including those known as ZSM catalysts, are suitable for selectively producing para substituted benzene derivatives upon being modified for that purpose. It is stated that one of the disadvantages of these catalysts is that they must often be modified with promoters to obtain significantly increased para-selectivity, i.e., that these types of catalysts have little or no intrinsic para-selectivity.
U.S. Pat. No. 4,548,914 discloses, inter alia, a method of enhancing the para-selectivity of a zeolite catalyst which is modified with one or more metal oxides in combination with phosphorus oxide. The patent discloses using the modified zeolite catalyst to produce the para-dialkylbenzene isomer.
U.S. Pat. No. 4,434,299 discloses, inter alia, a process for the production of aromatic amines by reaction of an alicyclic alcohol with ammonia in the presence of a catalyst wherein the catalyst is a crystalline silicate zeolite.
U.S. Pat. No. 3,231,616 discloses the production of aromatic amines, such as aniline, under continuous vapor phase operation by ammonolysis in the presence of an aluminum silicate catalyst, broadly known as zeolite.
U.S. Pat. No. 3,251,897 discloses the alkylation of hydrocarbons or substituted hydrocarbons in the presence of a zeolite catalyst.
The article entitled "Alkylation on Synthetic Zeolites" by Yashima et al, Journal of Catalysis, Vol. 16, pp. 273-280 (1970), noted in U.S. Pat. No. 4,080,395, discusses the catalytic activity of zeolite Y during the alkylation reaction of toluene with methanol. The article concludes that p-xylene can be selectively obtained using highly active zeolite catalysts.
The article entitled "Alkylation on Synthetic Zeolites" by Yashima et al., Journal of Catalysis, Vol. 26, pp. 303-312 (1972), noted in U.S. Pat. No. 4,115,434, discusses the alkylation of toluene with methanol and formaldehyde on alkali cation exchanged zeolites.
The article entitled "Industrial Application of Shape-Selective Catalysis"by N. Y. Chem and W. E. Garwood, Catal. Rev. Sci. Eng., 28 (2&3), 185-264 (1986), discloses, inter alia, shaped selective catalysis based on zeolites including with respect to obtaining para-selective reactions.
Additional patents which discloses the production of a hydrocarbon, such as a dialkylbenzene, utilizing a modified zeolite catalyst having high para-selectivity are as follows.
______________________________________ 3,728,408 4,275,256 4,469,806 4,478,949 4,007,231 4,370,508 4,472,518 4,486,616 4,080,395 4,391,739 4,477,583 4,532,226 4,080,396 4,391,998 4,477,584 4,581,215 4,090,981 4,409,132 4,477,585 4,593,137 ______________________________________
none of this latter group of patents specifically discloses the zeolite containing catalyst as suitable for use in connection with an amine.
Accordingly, zeolites as apparent from the hereinbefore noted patents and literature publications have been found to have activity for a variety of reactions, particularly the carbonium reaction. The source of carbonium-ion activity in the zeolite is believed to reside in the acidic characteristics of the structure. Zeolite acidity, in turn, depends on the nature of cation present, the extent of ion exchanged, the Si/Al ratio of the lattice, the heat treatment of the zeolite, and the amount of water present. This acidity is believed to be constituted by both Bronsted acids and Lewis acids. The reaction selectivity of the zeolites is believed to be due, at least in major part, to the three-dimensional framework of silica and alumina tetrahedra. This framework, as recognized in the art, can take many different configurations depending on how the tetrahedra are arranged and joined together and how much AlO.sub.4 is substituted for SiO.sub.4. The tetrahedra are arranged so that sizable cavities, channels, or cages exist within the structure. This framework or shape can be adjusted to fit different size molecules of reactants, products, or intermediates. The catalytic behavior of zeolites, including their selectivity, is applicable to both vapor-phase and liquid-phase reactions of different kinds of hydrocarbons and their derivatives.
Although there has been extensive activity with respect to the use of zeolites for selective reactions, no one to date has used the zeolites for the selective aniline alkylation with alkanols, nor has anyone to date recognized the temperature dependence of selective aniline alkylation in the presence of zeolites.